Process for breaking petroleum emulsions



Patented July 18, 1e

PROCESS FDR BIKE @l'- G PETROLEUM SIGNS Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo.,

assiors to Petrolite CorporatiomLtd Wilmington, DeL, a

corporation oi Delaware No Drawing. Application June 15, 1942, Serial No. 4 37455 8 Claims.

This invention relates primarily to the resolution of petroleum emulsions.

The main object of our invention is to provide a novel process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, "roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil'which constitutes the continuous phase of the emulsion.

Another object is to provide an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude petroleum and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned is of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

We have discovered that if one oxyallrylates glycerol so as to introduce at least three oxyalkylene radicals for each hydroxyl group, and if the product so obtained is reacted with a polybasic carboxy acid having not over eight carbon atoms, and in such a manner as to yield a fractional ester, due to the presence of at least one free carbdxyl radical, one can then esterify said acidic material or intermediate product with at least one mole of an alcoholic compound of the type herein described to give a variety of new compositions of matter which are eficient demulsifiers for crude oil emulsions.

The compounds used as clemulsifiers in our hereindescribed process, may be produced in any suitable manner, but are usually manufactured by following one of two general procedures. In one of said procedures the oxyalkylated glycerol, which is, in essence, a polyhydric alcohol, is reacted with a polybasic acid so as to give an acidic material or intermediate product, which, in turn, is reacted with an alcoholic body of the kind hereinafter described. and momentarily indicated by the formula R1(OH)m. Generically, the alcoholic body hereincontemplated may be considered a member of the class in which 712. may vary from 1 to 10, although the specific significance of m in the present instance will be hereinafter indicated. The second procedure is to react an alcohol of the formula type R1(OH)111. with a polybasic acid so as to produce an intermediate product, and then react said intermediate product or fractional ester with the selected oxyalkylated glycerol.

Glycerol may be conveniently indicated by the following formula:

If treated with an oxyalkylating agent, and momentarily consideration will be limited to an oxyethylating agent, one may obtain an oxyethylated glycerol of the following formula type:

in which the value of n may vary from 3 to 10 and all the values of 11. need not be identical. If a polybasic carboxy acid be indicated by the formula coon coon

then the acyclic reaction product of one mole of oxyethylated glycerol and one mole of a polybasic carboxy acid may be indicated by the following formula:

(OgHAO)n'OOCR(COOH)" CaHsOa-(C:H40)H oinlon n in which n" has the value of one or two. Similarly, if two moles of the polybasic acid be used,

then the compound may be indicated by the following formula:

in which a: is 0, 1 or 2, y is 0, 1 or 2, and'z is 1, 2 or 3, and x is 0 or 1, and y is 1 or 2.

It has been previously stated that compounds of the type herein contemplated may be obtained by oxyalkylating agents, without being limited to ethylene oxide. Suitable oxyalkylating agents include ethylene oxide, propylene oxide, butylene oxide and glycid, which, although not included, strictly speaking, by the unitary structure Cnmno, is included within the meaning of the hereto appended claims and may be simply considered as a variant ofpropyiene oxide, 1. e., hydroxypropylene oxide. Similarly, where a carboxylic hydrogen atom appears, it may be replaced by metal, an ammonium radical, or substituted ammonium radical, or by an organic group derived from an alcohol, such as an aliphatic alcohol, an aralkyl alcohol, or an alicyclic alcohol. It may also be converted into an amide, including a polyaminoamide. Thus, the preceding formula may be rewritten in its broader scope, as follows:

in which n replaces the numbers 2, 3 or 4, Z includes the acidic hydrogen atom itself. In the above formula and hereafter, for convenience, R1

' is intended to include any hydroxyl groups that cedures can be carried out in various manners,

but generally speaking, esteriflcations can be carried out at the lowest feasible temperaturesby using one of. several procedures. One procedure is to pass an inert dried gas through the mass to be esterifled, and have present at the same time a small amount of a catalyst,.such as dried.

HCl gas, a dried sulfonic acid, or the like. Another and better procedure, in many instances, is to employ the vapors of a suitable liquid, so as to remove any water formed and condense both the vapors of the liquid employed and the water in such a manneras to trap out the water and return the liquid to the reacting vessel. This procedure is commonly employed in the arts, and for convenience, reference ismade to U. 8. Patent No. 2,264,759, dated December 2, 1941, to Paul C. Jones.

Referring again to the last two formulas indicating the compoundsunder consideration, it can be readily'understood that such compounds, in numerous instances, have the property of polyfunctionality. In. view of this f act,-where there is at least one residual carboxyl and at least one residual hydroxyl, one would-expect that under suitable conditions, instead of obtaining the monomeric compounds indicated..one would in reality obtain a polymer in the sense, forexample, that polyethylene glycols represent a polymer of ethylene glycol. The term .-polymer is frequently used to indicate the polymerized product derived from a monomer in which the polymer has the same identical composition as the monomer. In the present instance, however, polymerization involves the splitting and loss of water so that the proc'essis essentially a self-esteriflcation. Thus, strictly speaking, the polymeric compounds are not absolutely polymers of the monomeric compounds, but since, 'forall practical purposes, they can be so indicated, and since such practice is common in the arts concerned with materials of this type, it is so adopted here. Thus, reference in the appended claims to polymers is intended to include the self-esterification products of the monomeric compounds. .0

In view of what has been said, and in view of the recognized hydrophile properties of therecurring oxyalkylene linkages, particularly the oxyethylene linkage, it is apparent that the mate-. rials herein contemplated may vary from co: 1- pounds which are clearly water-soluble through self-emulsifying oils, to materials which arr,- halsam-like and sub-resinous or semi-resinous in nature. The compounds may vary from monomers to polymers, in which the unitary structure appears a number of times, for instance 10, or 12 times. It is to be noted that'true resins, i. e., truly insoluble materialsoi' a hard plastic nature, are not herein included. In other words, the polymerized compounds are soluble to a fairly definite extent, for instance, at least 5% in some solvents, such as water, alcohol, benzene, dichloroethyl ether, acetone, cresylic acid, acetic acid, ethyl acetate, dioxane, or the like. This is simply another way of stating that the polyn erized product contemplated must be of the subresinous type, which is commonly referred to as an A resin, or a B resin, as distinguished from a C resin, which is a highly infusible, insoluble resin (see Ellis, Chemistry of Synthetic Resins 1935), pages 862, et seq).

Reviewing the form as presented, it is obvious thatone may obtain compounds within the scope disclosed, which contain neither a free hydroxyl nor a free carboxyl group, and one may also obtain a compound of the type in which there is present at least one free carboxyl, or at least one free hydroxyl, or both. The word "polar" has sometimes been used in the arts in this particular sense to indicate the presence of at least one free hydroxyl group, or at least one free carboxyl group, or both. In the case of the free carboxyl group, the carboxylic hydrogen atom may, of course, be replaced by any ionizable hydrogen atom equivalent, such, for-example, as a metal, an ammo-alum radical, a substituted ammonium radical, etc. In the hereto appended claims the word polar is used in this specific sense.

We are aware that compounds similar to those contemplated in the present instance may be derived from polyhydroxylated compounds having more than three hydroxyl groups. For instance, they may be derived from acyclic diglyceroL-triglycerol, tetraglycerol, mixed polyglycerols, mannitoi, sorbitol, various hexitols, dulcitol, pentaerythritol, sorbitan, mannitan, dipentaerythritol monoether, and other similar compounds. Such particular types in which higher hydroxylated materials are subjected to oxyalkylation and then employed in the same manner as oxyalkylated glycerol, is employed in the present instance, are not contemplated in this specific case, although attention is directed to the same.

Reference is also made to other oxyalkylated compounds which may be used as reactants to replace oxyalkylated glycerol, or oxyalkylated ethylene glycol, which latter reactant is described in a co-pending application hereinafter referred to. The reactants thus contemplated include the type in which there is an amino or amido nitrogen atom. Particularly, when present in a low molal .type of compound prior to oxyalhlation,

reference being made to polyhydroxylated matethree hydroxyl groups. For instance, the oxyalkylated derivatives, particularly the oxyethylated derivatives of ethyldiethanolamine, bis (hydroxymethyDacetamide, the acetamide of trishydroxymethyl) aminomethane, tetrahydroxylated ethylene diamine, etc. Compounds may also be derived from cyclic diglyceroi and the like.

Furthermore, for convenience, attention is dirooted to a somewhat similar class of materials which are described in U. S. Patent No. 2,295,170, dated September 8, 1942, to De Groote and Keiser. Said patent involves the use of the same type oi alcoholic bodies for reactants, but is limited. among other things, to the compounds which are essentially symmetrical in nature, for instance, involving the introduction of two alcoholic residues, whereas, in the present instance, one, two, or three, or more, might be introduced.

As indicated previously, the polybasic acids employed are limited to the type having not more than eight carbon atoms, for example, oxalic, malonic, succinic, glutaric, adipic, maleic, and phthalic. Similarly, one may employ acids such as iumaric, glutaconic, and various others, such as citric, malic, tartaric, and the like. The selection of the particular tribasic or dibasic acid employed, is usually concerned largely with the convenience of manufacture of the finished ester, and also the price oi the reactants. Generally speaking, phthalic acid or anhydride tends to produce resinous materials, and greater care must be employed if th ultimate or final product be of a sub-resinous type. Specifically, the preferred type of polybasic acid is such as to contain six carbon atoms or less. Generally speaking, the higher the temperature employed, the easier it is to obtain large yields of esterifled product, although polymerizationmay be stirrinlated. Oxalic acid may b comparatively cheap, but it decomposes readily at slightly above the boiling point of water. For this reason it is more desirable to use an acid which is more resistant to pyrolysis. Similarly, whena Dolybasic acid is available in the form of an anhydride, such anhydride-is apt to Produce the ester with greater case than the acid itself. For this reason, maleic anhydride is particularly adaptable, and also, everything else considered, the cost is comparatively low on a per molar basis, even though somewhat higher on a per pound basis. Suocinlc acid or the anhydride has many attractive quaiities of maleic anhydride, and this is also true of adipic acid. For purposes of brevity. the bulk of the examples, hereinafter illustrated, will refer to the use of maleic anhydride, although it is understood that any other suitable polybasic acid may be employed. Furthermore, reference is made to derivatives obtained by oxyethylation, although, as previously pointed out, other oxyallnvlating agents may be employed.

rm far as the range of oxyethylated glycerols employed as reactants is concerned, it is our preference to employ those in which approximately to 24, oxyethylene groups have been introduced into a single glycerol molecule. This means that approximately five to eight oxyethylene radicals have been introduced for each original hydroxyl group.

The oxyalkylation of glycerol is a well brown procedure see Example 11 of German Patent No. 605,973, dated November 22, 1934, to I. G. Fatbenindustrie Akt. Ges.). The procedure indicated in the following three examples is substantially identical with that outlined in said aforementioned German patent.

Oxvs'rma'ra GLYCEROL Example 1 184 pounds of glycerol is mixedwith 42%, by weight, of caustic soda solution having a specific gravity of 1.383. The caustic soda acts as a catalyst. The ethylene oxide is added in relatively small amounts, for instance, about 44 pounds at a. time. The temperature employed is from C. Generally speaking, the gauge pressure during the operation approximates 200 pounds at the maximum, and when reaction is complete, drops to zero, due to complete absorption of the ethylene oxide. When all the ethylene oxide has been absorbed and the reactants cooled, a second small portion, for instance, 44 more pounds oi ethylene oxide, are added and the procedure repeated until the desired ratio of 15 pound moles of ethylene oxide to one pound mole of glycerol is obtained. This represents 660 pounds of ethylene oxide for 92 pounds of glycerol.

Oxvarnvmrao GLYCEROL I Example 2 The ratio of ethylene oxide is increased to 18 pound moles for each pound mole oi. glycerol. Otherwise, the same procedure is followed as in Example 1, preceding.

Gxvarnxmrrn GLYCEROL Example 3 v The same procedure is followed as in the two previous examples, except that the ratio of ethylene oxide to glycerol is increased to 121 to one.

@XYETHYLATED GLYcaxoi. MALuA'rp Ezmmple 1 Oxramvmrau GLYcnRoL Manners:

Example 2 The same procedure is iollowed as in the preceding example, except that two moles of maleic anhydride are employed so as to obtain the dimaleate instead of the monomaleate.

OxYs'rHYLArso GLYCEROL MALEATE Example 3 The same procedure is followed as in the two preceding examples, except that three moles of maleic. anhydride are employed so as to obtain the triinaleate.

Oxvarrrvmran GLYCEROL MALEATE Example 4 The same procedure is employed as in the preceding examples, except that oxyethylated glycerol (ratio 1 to 18) is substituted in place oi oxyethylated glycerol (ratio 1 to 15).

OXYETHYLATED GLYCEROL MALEATE Example 5 The same procedure is employed as in the preceding examples, except that oxyethylated glycerol (ratio 1 to 21) is employed instead of oxyethylated glycerol (ratio 1 to 15) or (1 to 18).

Previous reference has been made to an alcoholic body which has been defined generically by the formula R1(OH)m. The sub-generic class of alcoholic compounds employed as reactants in the manufacture of the present compounds, are materials commonly referred to as the amides of high molal alcoholic acids, or high molal hydroxy acids. 'Such amides are derived from the high molal hydroxy acids. Like the high molal hydroxy acids, 'they are invariably water-insoluble.

Since the amides are derivatives of the high molar hydroxy acids, it is most convenient to indicate the variety of high molar hydroxy acids which may be converted into amides or substituted amides. The commonest example of a high molal hydroxy acid is ricinoleic acid. Other hydroxy fatty acids include hydroxystearic acid, dihydroxystearic acid, diricinoleic acid, aleuritic acid, and the like. Similar acids are obtained in the oxidation of paraffln, petroleum hydrocarbons, or wax, and are commonly referred to as hydroxylated wax acids. Hydroxylated wax acids occur as by-products in the oxidation of waxes or similar materials, and are usually separated so that the commonest commercial form of oxidized wax acids represent mixtures comparatively free from the hydroxylated compounds. other procedures, such as chlorination, either by 1 addition or substitution, as, for example, chlorination of oleic acid or stearic acid. Subsequent reactions involve the removal of the chlorine with the introduction of a hydroxyl radical.

Undecylenic acid derived from castor oil, has been converted into a hydroxy undecenoic acid. Unsaturated hydroxy acids, such as ricinoleic acid, may be treated in various manners, so as to produce derivatives, for example, chlorinated or brominated ricinoleic acid. Such materials are entirely satisfactory for use as reactants in the preparation of materials of the kind herein contemplated. Naturally-occurring napthenic acids can also be converted into hydroxylated products by following similar procedure. An unsaturated hydroxy acid, such as ricinoleic acid, can be converted into a hydroxylated arylstearic acid. Such procedure contemplates reactions such as those involving ricinoleic acid, benzene, and

aluminum chloride in large excess, or involvesthe desulfonation of a sulfo-aromatic fatty acid. In any event, by employing derivatives of undecylenic' acid, or one or more of the various wax acids, naturally-occurring naphthenic acid, ricinoleic acid, d-iricinoleic acid, or derivatives thereof, as previously explained, one can obtain a variety of hydroxylated monocarboxy acids, having at least 11 carbon atoms and not in excess of- 36 carbon atoms. Such compounds are the kind herein contemplated as reactants to furnish the alcoholiform hydroxyl.

Hydroxy acids of the kind herein contemplated as reactants for the formation of amides, may also be prepared by the hydrolysis ofalphahalogenacids. For instance, alpha-bromocaproic acid, alpha-bromocaprylic acid, alphabromocapric acid, alpha-blomolauric acid, alphabromomyristi'c acid, alpha-bromopalmitic acid, and the like, can be hydrolyzed to give the corresponding alpha-hydroxy acid. Indeed, a reactive alpha-halogen acid may serve as a functional equivalent ofan alpha-hydroxy acid by liberation of hydrochloric acid, instead of water. Such type of reaction, however, involves numerous difficulties; and thus, it is better to employ a hydroxy acid.

-Ellis; and 2,177,407, dated Oct. 24, 1939, to Hansascaeas In some instances derivatives of hydroxylated unsaturated acids are most readily obtained by the employment of an intermediate in which the hydroxyl group is protected. Thus, ricinoleic acid may be acetylated, and such acetyl ricinoleic acid converted into a derivative, for instance, a derivative in which an aryl group is introduced. Such derivatives can then be saponifled or hydrolyzed so as to regenerate the hydroxyl radical.

If a hydroxylated acid ester, for instance, methyl ricinoleate, is treated with an oxyalkylating agent, such as ethylene oxide, propylene oxide, or the like, there seems to be some change in the hydroxyl group, somewhat akin to the solubilizing action which takes place in respect to high molal primary alcohols under the same condition, for instance,the solubilizing of cetyl alcohol. However, possibly for reasons of steric hindrance, or because the alcoholic hydroxyl is a secondary hydroxyl, true solubilization does not appear to be obtainable. If such oxyalkylated ester is then saponifled to regenerate the acid, i. e., a water-insoluble oxyalkylated ricinoleic acid, such material or similar materials may be used as reactants in the present instance to produce amides of the kind herein contemplated as raw material.

The manufacture of amides from acids is, of course, comparatively simple. One may employ the acid or asuitable derivative, such as the acyl halide or preferably, the ester. In many instances it is easier to obtain the amide from an ester derived from a monohydric or polyhydric alcohol than it is from the acid itself.

As to the manufacture of various esters from acids of the kind above described, attention is directed to the following United States patents, to wit: No. 1,160,595, dated Nov. 16, 1915, to Gruter et al.; 2,221,674, dated Nov. 12, 1940, to

ley. See also Organic Syntheses, volume X, page 88.

In any event, the acid or suitable derivative, particularly the ester, is treated with ammonia to produce the amide.

The method of manufacturing the'amide requires no elaboration, but simply as illustrative of the art, reference is made to U. S. Patent No. 2,058,013, to Henke and Zertman, dated October 20, 1936.

As to the procedure for manufacture of substituted amides, reference is made to the following United States patents, i. e., Nos. 2,013,108, dated Sept." 3, 1935, to Reppe et al.; 1,475,477, dated Nov. 27, 1923, to Ellis; and 1,954,433, dated Apr. 10, 1934, to-Thomas etal.

If low mol'al' amines, particularly prima amines for example, butylamine, amylamine, aniline, cyclohexylamine, or the like, are substituted for ammonia, one obtains a substituted amide which can be employed satisfactorily in the present process, provided, of course, that the final product is water-soluble. In fact, secondary amines, such as dibutylamine and diamylamine, can be used. Since such materials are generally more expensive than ammonia, and since the hydrocarbon groups piesent tend to decrease water solubility, there is no added advantage in using such materials, except for some special purpose, such as the resolution of oil field emulsions; If such materials are used, it is preferable that they be derivatives of primary amines, i. e., that the substituted amide contain only one hydrocarbon group, and in any asaaees event, that such hydrocarbon group contain not more than 7 carbon atoms, as, for example,

derivatives of monoamylamine, cyclohexylamine, I

COMPLETED MONOMERIC DERIVATIVE Example 1 One pound mole. of a product of the kind described under the heading Oxyethylated glycerol maleate, Example 1" is reacted with one pound mole of ricinoleoamide, preferably in the absence of any high boiling hydrocarbon or inert solvent. However, if an inert vaporizing solvent is employed, it is generally necessary to use one which has a higher boiling range than xylene, and

sometimes removal .of such solvent mightpresent a difficulty. In other instances, however, such high boiling inert vaporizing solvent, if employed, might be permitted to remain in the reacted mass and appear as a constituent or ingredient of the final product. In any event, our preference is to conduct the reaction in the absence of any such solvent and permit the reaction to proceed with the elimination of water. The temperature of reaction is about 180 to 200 C. and time of reaction about 20 hours.

COMPLETED MONOMERIC DERIVATIVE Example 2 The same procedure is followed as in Com= pleted Monomeric Derivative, Example 1, preceding, except that the dimaleate described under the heading Oxyethylated glycerol maleate, Example 2," is used instead of the monomaleate.

CoMeLETEn Mo'NomERIc DERIVATIVE Example 3 The'same procedure is followed as in the two preceding examples, except that the trimaleate is substituted for the monomaleate or the dimaleate in the two preceding examples.

COMPLETED MONOMERIC DERIVATIVE Example 4 COMPLETED MoxomERIc DERIVATIVE Example 5 The same procedure is followed as in Example 3, preceding, except that for each pound mole of trimaleate, instead of adding one pound mole of ricinoleoamide, one adds three pound moles of ricinoleoamide for reaction.

Com are Monounnrc DEeIvA-rIvE Example 6 Reference to the preceding examples will show that in each and every instance oxyethylated glycerol (ratio 1 to 15) has been employed as a raw material'or primary reactant. In the present instance, a more highly oxyethylated glycerol is employed, to wit, one involving the ratio of 1 to 18. (See Oxyethylated glycerol maleate, Example 4, preceding).

' Compare!) MONOMERIC DERIVATIVE Example 7 The same procedure is followed as in Example 6, immediately preceding, except that the oxyetlwlated glycerol employed represents one having an even higher degree of oxyethylation. For example, one indicated by the ratio of l to 21. (See Oxyethylated glycerol maleate, Example 5, preceding).

COMPLETED MONOMERIC DERIVATIVE Example 8 A mixture of hydroxylated oxidized wax acids having an average molecular weight of approximately 250-275 is converted into the corresponding mixture of amides and substituted for ricinoleoamide, in Examples 1 to 7, immediately preceding.

COMPLETED MONOMERIC DERIVATIVE Example 9 A mixture of hydroxylated oxidized wax acids having an average molecular weight of approximately 275-300 is converted into the corresponding mixture of amides and substituted for ricinoleoamide, in Examples 1 to 7, immediately preceding.

Comte-rep Moxommuc DERIVATIVE Example 10 A mixture of hydroxylated oxidized wax acids having an average molecular weight of approximately 300-325 is converted into the corresponding mixture of amides and substituted for ricinoleoamide. in Examples 1 to 7, immediately pre ceding.

COMPLETED MONOHERIC DERIVATIVE Example 11 Dihydroxystearamide is subst tuted for rlcin-= oleoamide in Examples 1 to 7, immediately preceding.

The method of producing such fractional esters is well known. The general procedure is to em ploy a. temperature-above the boiling point of water and below the pyrolytic point of the reactants. The products are mixed and stirred constantly during the heating and esteriflcation step. If desired, an inert gas, such as dried nitrogen or dried carbon dioxide, may be passed through the mixture. Sometimes it is desirable to add an esteriiication catalyst, such as sulfuric acid, benzene sulionic acid, or the like. This is the same general procedure as employed in the manufacture of ethylene glycol dihydrogen diphthalate. (8ee U. 8. Patent No. 2,075,107, dated March 30, 1937, to Frasier.)

Sometimes esteriflcation is conducted most readily in the presence of an inert solvent, that carries away the water of esterification which may be formed, although as is readily appreciated, such water of esteriflcation is absent when such type of reaction involves an acid anhydride, such as maleic anhydride, and a glycol. However, if water is formed, for instance, when citric acid is employed, then. a solvent such as xylene may be present and employed to carry off the water formed. The mixture of xylene vapors and water vapors can be condensed so that the water is separated. The xylene isthen returned to the reaction vessel for further circulation. This is a conventional and well-known procedure and requires no further elaboration.

In the previous monomeric examples there is a definite tendency, in spite of precautions, at

least in a number of instances, to obtain polymeric materials and certain cogeneric by-products. This is typical, of course, of organic reactions of this kind, and as is well known, organic reactions per se are characterized by the fact that 100% yields are the exception, rather than the rule, and that significant yields are satisfactory, especially in those instances where the byproducts or cogeners may satisfactorily serve with the same purpose as the principal or intentional product. This is true in the presen instance. In many cases when the compound is manufactured for purposes of demulsification, one is better oil to obtain a polymer in the sense previously described, particularly a polymer whose molecular weight is a rather small multiple of the molecular weight of the monomer, for instance, a polymer whose molecular weight is two, three, four, five, or six times the molecular weight of the monomer. Polymerization is hastened by the presence of an alkali, and thus in instances where it is necessary to have a maximum yield of the monomer, it may be necessary to take such precautions that the alkali used in promoting oxyethylation of glycerol, be' removed before subsequent reaction. This, of course, can be done in any simple manner by conversion to sodium chloride, sodium sulfate, or any suitable procedure.

In the preceding examples of the Completed monomeric derivative, Examples 1 to 10, inclusive, no reference is made to the elimination of such alkaline catalyst, in view of the efiectiveness of the low multiple polymers as demulsifiers. Previous reference has been made to the fact that the carboxylic hydrogen atom might be variously replaced by substituents, including organic radicals, for instance, the radicals obtained from alcohols, hydroxylated amines, non-hydroxylated amines, polyhydric alcohols, etc. Obviously, the reverse is also true, in that a free hydroxyl group may be esterifled with a selected acid, varying from such materials as ricinoleic acid to oleic acid, including alcohol acids, such as hydroxy acetic acid, lactic acid, ricinoleic acid and also polybasic acids of the kind herein contemplated.

With the above facts in mind, it becomes obvious that what has been previously said as to polymerization, with the suggestion that byproducts or cogeneric materials were formed, may be recapitulated with greater definiteness, and one can readily appreciate that the formation of heat-rearranged derivatives or compounds must take place to a greater or lesser degree. Thus, the products herein contemplated may be characterized by being monomers of the type previously described, or esterification polymers, or the heat-rearranged derivatives of the same,

and thus including the heat-rearranged derivatives of boththe polymers and esteriflcation monomers, separately and Jointly. Although the class of materials specifically contemplated in this instance is a comparatively small and narrow class of a broad genus, yet it is obviously impossible to present any adequate formula which would contemplate the present series in their complete ramification, except in a manner employed .in the hereto appended claims.

Although the products herein contemplated vary so broadly in their characteristics, 1. e., monomers through sub-resinous polymers, soluble products, water-emulsifiable oils or compounds, hydrotropic materials, balsams, sub-resinous ma.- terials, semi-resinous materials, and the like, yet

. there is always present the characteristic unitary hydrophile structure related back to the oxyalkylation, particularly the oxyethylation oi the glycerol used as the raw material. As hereinafter indicated, in practising our process, the demulsifier may be added to the emulsion at the ratio of 1 part in 10,000, 1 part in 20,000, 1 part in 30,000, or for that matter, 1 part in 40,000.

In such ratios it well may be that one cannot differentiate between the solubility of a compound completely soluble in water in any ratio, and a semi-resinous product apparently insoluble in water in ratios by which ordinary insoluble materials are characterized. However, at such ratios the importance must reside in interfacial position and the ability to usurp, preempt, or replace the interfacial position previously occupied perhaps by the emulsifying colloid. In any event, reviewed in this light, the obvious common property running through the entire series, notwithstanding variation in molecular size and physical make-up, is absolutely apparent. Such statement is an obvious oversimpliflcation of the rationale underlying demulsification, and does not even consider the resistance of an interfacial film to crumbling, displacement, being forced into solution, altered wetability and the like. As to amidification polymers, for instance, where Z is a polyaminoamide radical, see what is said subsequently.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HaAr-Rmnalmcen Cocsmms Example 1 COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERS Example 2 The same procedure is followed asin the preceding example, except that polymeriz ation is continued, using either a somewhat longer reaction time, or it may be a somewhat higher temperature, or both, so as to obtain a material having a molecular weight of approximately three to four times that of the initial product.

seem

COMPLETED POLYMERIC DERIVATIVES INCLUDING e HEAT-REARRANGED COGENERS Example 3 The same procedure is followed as in Examples 1 and 2, preceding, except that the monomer is derived from one pound mole of oxyethylated glycerol, which has been treated with three pound moles of maleic anhydride and then with two pound moles of dihydroxystearamide.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGEHERS Example 4 The same procedure is followed as in Examples 1 to 3, preceding, except that one polymerizes a mixture instead of a single monomer, for instance, a mixture of materials of the kind described in Completed monomeric derivative, Example 3, and in Completed monomeric derivative, Example 4, are mixed in molecular proportion and subjected to polymerization in the manner indicated in the previous examples.

It is understood, of course, that the polymer-, ized product need not be obtained as a result of a two-step procedure. In 'other' words, one need not convert the reactants into the monomer and then subsequently convert the monomer into the polymer. The reactants may be converted through the monomer to the polymer, in one step. Indeed, the formation of the monomer and "polymerization may take place simultaneously. This is especially true if polymerization is conducted in the absence of a liquid such as xylene, as previously described, and if one uses a comparatively higher temperature, for instance, approximately 220" C. for polymerization. Thus, one pound mole of oxyethylated glycerol maleateof the kind described, ratio 1 to 15, up to 1 to 21, is mixed with two moles of ricinoleoamide and reacted for 30 hours at approximately 220 C. until the mass is homogeneous. It'is stirred constantly during reaction. Polyfunctionality may reside in dehydration (etherization) of two hydroxyl groups attached to dissimilar molecules.

The fact that the polymerized heat-rearranged products can be made in 'aisingle step, illustrates a phenomenon which sometimes occurs either in such instances where alcoholic bodies of the kind herein illustrated are contemplated as reactants, or where somewhat kindred alcoholic bodies are employed. The reactants may be mixed mechanically to give a homogeneous mixture, or if the reactants .do not mix to give a homogeneous mixture, then early in the reaction stage there is formed, to a greater or lesser degree, sufiicient monomeric materials so that a homogeneous system is present. Subsequently, as reaction continues, the system may become heterogeneous and exist in two distinctphases, one being possibly an oily body of moderate viscosity, and the other being a heavier material, which is sticky or sub-resinous in nature. In many instances, it will be found that the thinner liquid material is a monomer and the more viscous or resinous material is a polymer, as previously described.- Such product can be used for demulsification -by adding a solvent which will mutuallyfdissolve the two materials-or else, by separating the two heterogeneous phases and employing each as if it were a separate product of reaction. 7

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, orafter dilution with any suitable solvent,

such as water; petroleum hydrocarbons such as gasoline, kerosene, stove oil, a coal tar product such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining ofpetroleum,.etc., may be employed as diluents. Similarly, the material or materials herein described, maybe admixed with one or more of the 'solvents customarily used in connection with conventional demulsifying agents, provided that such compounds are compatible. They will be compatible with the hydrophile type of solvent in all instances. Moreover, said material or materials may be used alone, or in admixture with other suitable well known classes of demulsifying agents. 1

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oil and water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to 30,000, such an apparent insolubility in oil and water is not significant, because said reagents undoubtedly have solubility within the concentration em- 1 ployed. This same fact is true in regard to the material or materials herein described, except that they are invariably water-soluble.

We desire to point out that the superiority of the reagent or demulsifying agent contemplated in our herein described process for breaking petroleum emulsions, is based upon its ability to treat certain emulsions more advantageously and at a somewhat lowercost than is possible with other available demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsifying agent or treating agent herein described will .find comparatively limited application, so far as the majority of oil field emulsions are concerned; but we have found that such a demulsifying. agent has commercial value, as it will economically break or resolve oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the demulsifying agents heretofore available.

-In practising our improved process for resolving petroleum emulsions of the water-in-oil type, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated,

in any of the various ways, or by any of the various apparatus now generally used to reso ve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone, or in combination with other demulsifying procedure, such as the electrical dehydration process.

The demulsifier herein contemplated maybe employed in connection with what is commonly known as down-the-hole procedure, 1. e., bringing the demulsifier in contact with the fluids of the well at the bottom of the well, or at some point prior to their emergence. This particular type of applicatielr is decidedly-feasible when the deed in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

aforementioned polymers, separately and jointly, and of the following formula:

[(mmonoooncoozp C3H6 3[( i )n -]I clnlowoocncoorm. in which R. is a carboxyl-free radical of a dibasic carboxy acid having not over 6 carbon atoms; R; is a water-insoluble high molal hydroxy acid amide radical having 18 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3 to 10; :1: represents the numerals .0

. to 2; 11 represents the numerals 0 to 2; and a represents the numerals 1 to 3.

'7. A process for breaking petroleum emulsions of the water-in-oil type, characterized by sub- Jecting the emulsion to the action of a demulsim which R is a carboiwl-free radical of 'a dibasic c'arboxy acid having not over 6 carbon atoms; R1 is a water-insoluble high molal unsaturated hydroxy acid amide radical having 18 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3 to 10; :1: represents the numerals 0 to 2; 11 represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

8. A process for breaking petroleum emulsions of tue water-in-oll type, characterized by subjecting the emulsion to the action of a demulsifier comprising a polar acidic member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formula: 

